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With hydrogenchloride; sodium nitrite; In water; at 0 - 5℃; for 2h;Product distribution / selectivity; |
Preparation of the diazonium: 9.0 g (40 mmol, 98.5%) of 2-amino-4-chloro-5-methyl- benzenesulfonic acid are stirred in 180 ml of deionised water, and 14 ml of aqueous 37% HCI are added thereto. The fine suspension is then cooled to a temperature of 0-5C by means of an ice bath, and 10 ml of a 4N sodium nitrite solution are added dropwise thereto. After 2 hours, 1.0 ml of 1 N sulfamic acid is added. Coupling: 13.2 g (40 mmol) of 4-acetoacetylaminonaphtholsulfonic acid sodium salt are dissolved in 200 ml of deionised water. The solution is cooled to a temperature of 0-5C and the above diazonium suspension is added dropwise thereto, the pH being maintained at 4.5-5.0 by means of a 30% sodium hydroxide solution. Any foam formation is suppressed with 5 ml of ethanol and 5 drops of Surfynol 104E. When the addition is complete, the reaction mixture is stirred at 0-5C for 2 hours and then at room temperature for 12 hours. The reaction mixture is divided into two samples, each of about 360 ml. The resulting yellow suspension of the first sample is filtered by means of hard filters, washed with 100 ml of water and dried in a vacuum cabinet at 90C. 10.3 g of the sodium salt of the compound of formula are obtained. The second portion of the suspension is heated to 80C. A solution of 3.5 g of cal- cium chloride (32 mmol) in 10 ml of deionised water is added thereto and the pH is adjusted to 8.0 with a small amount of sodium hydroxide solution. The mixture is then stirred at 80C for 2 hours. The resulting yellow suspension is filtered, while hot, through hard filters, washed with 200 ml of deionised water and dried in a vacuum cabinet at 90C. 10.5 g of the calcium salt of the compound of formula (101) are obtained, which colours PVC plastics in greenish-yellow shades. Example 5: Preparation of the diazonium: 4.5 g (20 mmol, 98.5%) of 2-amino-4-chloro-5-methyl- benzenesulfonic acid are stirred in 80 ml of deionised water, and 7 ml of aqueous 37% HCI are added thereto. The fine suspension is then cooled to a temperature of 0-5C by means of an ice bath, and 5 ml of a 4N sodium nitrite solution are added dropwise thereto. Then, after 2 hours, 1.0 ml of 1 N sulfamic acid is added. Coupling 6.6 g (20 mmol) of 4-acetoacetylaminonaphtholsulfonic acid sodium salt are dissolved in 60 ml of deionised water. The solution is cooled to a temperature of 0-5C and the above diazonium suspension is added dropwise thereto, the pH being maintained at 4.5-5.0 by means of a 30% sodium hydroxide solution. 30 ml of etha- nol and 1 ml of acetic acid are then added thereto. When the addition is complete, the reaction mixture is stirred at 0-5C for 2 hours. The mixture is then heated to 80C, a solution of 3.5 g of calcium chloride (32 mmol) in 10 ml of deionised water is added and the pH is adjusted to 8.0 with (a small amount of) NaOH. The mixture is then stirred for a further 2 hours at 80C. The resulting yellow suspension is filtered, while hot, through hard filters, washed with 300 ml of cold deionised water and dried in a vacuum cabinet at 90C. 10 g of the Ca2+/Na+ mixed salt of the compound of for- mula (101), which contains a little water, are obtained, which colours PVC plastics in greenish-yellow shades. Example 6: Preparation of the diazonium: 4.5 g (20 mmol, 98.5%) of 2-amino-4-chloro-5-methyl- benzenesulfonic acid are stirred in 80 ml of deionised water, and 7 ml of aqueous 37% HCI are added thereto. The fine suspension is then cooled to a temperature of 0-5C by means of an ice bath, and 5 ml of a 4N sodium nitrite solution are added dropwise thereto. Then, after 2 hours, 1.0 ml of 1 N sulfamic acid is added. Coupling: 6.6 g (20 mmol) of 4-acetoacetylaminonaphtholsulfonic acid sodium salt are dissolved in 60 ml of deionised water, and 1 ml of acetic acid is added. The solu- tion is cooled to a temperature of 0-5C and the above diazonium suspension is added dropwise thereto, the pH being maintained at 4.5-5.0 by means of a 30% ammonia solution. To suppress any foam formation, 25 ml of isopropanol are added. When the addition is complete, the reaction mixture is stirred at 0-5C for 4 hours. The mixture is then heated to 80C and adjusted to pH 8.0 with a 30% ammonia so- lution. The mixture is then stirred at 80C for 2 hours. The resulting yellow suspen- sion is filtered, while hot, through hard filters, washed with 1 litre of cold deionised water and dried in a vacuum cabinet at 90C. 9.2 g of the NH4+/Na+ mixed salt of the compound of formula (101) are obtained, which colours PVC plastics in yellow shades. |